Photoresist compositions

ABSTRACT

The present invention relates to a composition and a process for preparing a composition that comprises: a) a novolak resin partially esterified with from about 1 to about 7 weight percent (further from about 3 to about 7 weight percent) of a naphthoquinonediazidosulfonyl group; b) one or more dilution resins; c) at least one photosensitive component in an amount sufficient to photosensitize said composition; and d) at least one solvent.

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application is a continuation-in-part of U.S. patentapplication Ser. No. 10/404,612, filed Apr. 1, 2003, the contents ofwhich are hereby incorporated herein by reference.

BACKGROUND OF THE INVENTION

[0002] The present invention relates to a light-sensitive photoresistcomposition and a process for producing such a composition. Inparticular, the subject invention relates to a photoresist compositioncomprising: a composition comprising: a) a novolak resin partiallyesterified with from about 1 to about 7 weight percent of anaphthoquinonediazidosulfonyl group (further from about 3 to about 7weight percent); b) one or more dilution resins; c) at least onephotosensitive component in an amount sufficient to photosensitize saidcomposition; and d) at least one solvent. Such a photoresist compositionprovides a positive photoresist that exhibits low absorption for thickerfilms, good photospeed, adjustable contrast, good shelf life stability,low outgassing potential, substantially no crystallization, excellentcoating properties and broadband sensitivity.

[0003] Photoresist compositions are used in microlithography processesfor making miniaturized electronic components, such as in thefabrication of computer chips and integrated circuits. Generally, inthese processes, a thin coating of a film of a photoresist compositionis first applied to a substrate material, such as silicon wafers usedfor making integrated circuits. The coated substrate is then baked toevaporate any solvent in the photoresist composition and to fix thecoating onto the substrate. The baked-coated surface of the substrate isnext subjected to an image-wise exposure to radiation.

[0004] This radiation exposure causes a chemical transformation in theexposed areas of the coated surface. Visible light, ultraviolet (UV)light, electron beam and X-ray radiant energy are radiation typescommonly used today in microlithographic processes. After thisimage-wise exposure, the coated substrate is treated with a developersolution to dissolve a and remove either the radiation-exposed (in thecase of positive photoresist) or the unexposed (in the case of negativephotoresist) areas of the coated surface of the substrate.

[0005] There are two types of photoresist compositions, negative-workingand positive-working. When negative-working photoresist compositions areexposed image-wise to radiation, the a areas of the resist compositionexposed to the radiation become less soluble to a developer solution(e.g. a cross-linking reaction occurs) while the unexposed areas of thephotoresist coating remain relatively soluble to such a solution. Thus,treatment of an exposed negative-working resist with a developer causesremoval of the non-exposed areas of the photoresist coating and thecreation of a negative image in the coating thereby uncovering a desiredportion of the underlying substrate surface on which the photoresistcomposition was deposited.

[0006] On the other hand, when positive-working photoresist compositionsare exposed image-wise to radiation, those areas of the photoresistcomposition exposed to the radiation become more soluble to thedeveloper solution (e.g. a rearrangement reaction occurs) while thoseareas not exposed remain relatively insoluble to the developer solution.Thus, treatment of an exposed positive-working photoresist with thedeveloper causes removal of the exposed areas of the coating and thecreation of a positive image in the photoresist coating. Again, adesired portion of the underlying substrate surface is uncovered.

[0007] After this development operation, the now partially unprotectedsubstrate may be treated with a substrate-etchant solution or plasmagases and the like. The etchant solution or plasma gases etch thatportion of the substrate where the photoresist coating was removedduring development. The areas of the substrate where the photoresistcoating still remains are protected and, thus, an etched pattern iscreated in the substrate material that corresponds to the photomask usedfor the image-wise exposure of the radiation. Later, the remaining areasof the photoresist coating may be removed during a stripping operation,leaving a clean etched substrate surface. In some instances, it isdesirable to heat treat the remaining photoresist layer, after thedevelopment step and before the etching step, to increase its adhesionto the underlying substrate and its resistance to etching solutions.

[0008] Positive working photoresist compositions are currently favoredover negative working resists because the former generally have betterresolution capabilities and pattern transfer characteristics.Photoresist resolution is defined as the smallest feature that theresist composition can transfer from the photomask to the substrate witha high degree of image edge acuity after exposure and development. Inmany manufacturing applications today, resist resolution on the order ofless than one micron is quite common. In addition, it is almost alwaysdesirable that the developed photoresist wall profiles be near verticalrelative to the substrate. Such demarcations between developed andundeveloped areas of the resist coating translate into accurate patterntransfer of the mask image onto the substrate.

[0009] Efforts have been previously been made to attach DNQ groups tonovolak resins. However, these efforts have been directed towardproviding a resin that functions as both the film forming component andthe photosensitizer. This enables the production of single componentphotoresists because it is not necessary to add a separate photoactivecomponent to photosensitize the photoresist composition. One of thefirst patents relating to this technology was U.S. Pat. No. 3,046,120.An ortho-cresol/formaldehyde novolak resin was esterified with anaphthoquinone-(1,2)-diazide-(2)-5-sulfonyl chloride to provide a singlecomponent photosensitive composition that useful for the production ofprinting plates. Other patents that relate to these attempts to combinea photosensitive compound with a phenolic resin are U.S. Pat. Nos.3,635,709; 4,123,279 and 4,306,011.

[0010] U.S. Pat. No. 5,178,986 relates to a light sensitive mixtureuseful as a positive acting photoresist. The mixture contains a compoundthat comprises the reaction product of a DNQ and an oligomeric phenol.More recent attempts to provide a photoresist composition comprising theesterification product of a phenolic resin and a DNQ are described inU.S. Pat. No. 5,279,918. An ortho-quinone diazide sulfonyl chloride wascondensed with a relatively low molecular weight novolak resin, whereinfrom 40% to 90% of the phenolic hydroxy groups were condensed with theDNQ groups. This provided a high concentration of DNQ moieties on thenovolak resin backbone.

[0011] In U.S. Pat. No. 5,422,221 a photoresist composition is disclosedwherein the novolak resin serves as both the alkali-soluble film-formingresin and the photosensitive component of the composition. This isaccomplished by replacing the hydrogen atom of a hydroxyl group in thenovolak resin with a DNQ group in a proportion of 0.03 to 0.27 mol perhydrogen atom (believed to be equivalent to 3 to 27% esterification). Itwas disclosed that more than 0.27 mol % [sic] substitution results in anovolak resin that is less soluble in the photoresist solvent and thatless than 0.03 mol % [sic] substitution provides a novolak resin that istoo low in film retentivity so that the resulting photoresistcomposition cannot be patterned and is, therefore, useless.

[0012] U.S. Pat. No. 5,529,880 discloses a photoresist compositioncomprising: 1) the esterification product of a DNQ and a novolak resinhaving pendant phenol hydroxyl groups and 2) the esterification productof a phenol having 2 to 5 phenyl rings and at least 4 phenolic hydroxygroups with a DNQ having at least 50% of its phenol hydroxyl groupsesterified with the DNQ. The esterification reaction to produceesterification product 1) is controlled so that a maximum of 20% of thephenolic hydroxy groups are esterified.

[0013] U.S. Pat. No. 5,723,254 discloses a positive acting photoresistcomposition containing a mixture of photoactive components. Onecomponent of the mixture is the esterification product of a DNQ with alow molecular weight phenolic resin. Another component is theesterification product of a DNQ with a low molecular weight phenolhaving from 1 to 3 aryl rings and from 1 to 3 hydroxyl groups. A thirdphotoactive component that may be present is the esterification productof a DNQ with a relatively high molecular weight polyhydric polynuclearphenol.

SUMMARY OF THE INVENTION

[0014] The present invention relates to a photoresist composition thatcomprises a composition comprising: a) a novolak resin partiallyesterified with from about 1 to about 7 weight percent of anaphthoquinonediazidosulfonyl group (further from about 3 to about 7weight percent); b) one or more dilution resins; c) at least onephotosensitive compound in an amount sufficient to photosensitize saidcomposition; and d) at least one solvent.

[0015] The partially esterified novolak for the claimed composition is awater-insoluble, alkali-soluble, film forming phenolic resin preferablyhaving a weight average molecular weight from about 1,000 to 30,000,preferably from about 1,500 to 10,000. The DNQ used for partialesterification of the novolak resin contains quinonediazide sulfonylgroups that replace the hydrogen atom of hydroxyl groups in the novolakresin. The one or more dilution resins dilute the amount of partiallyesterified novolak resin in the composition to allow for bettersolution, viscosity, and other physical and chemical benefits in thecomposition and the resulting photoresist. The solvent suitable for usein present invention may be any of those well known to those skilled inthe art; solvent or solvent blends include those selected from2-heptanone, either alone or in combination with anisole; ethyl lactate,either alone or in combination with n-butyl acetate or propylene glycolmethyl ether; or propylene glycol methyl ether, either alone or incombination with ethyl 3-ethoxypropionate.

[0016] The invention further relates to a process of forming an image ona substrate. The substrate is coated with a film of the photoresistcomposition of the instant invention. The photoresist film is imagewiseexposed through a mask with ultraviolet radiation and processed inaccordance with those steps known to those skilled in the art.

[0017] The invention further relates to a method for producing amicroelectronic device by forming an image on a substrate comprising i)providing an admixture of a photoresist composition comprising: a) anovolak resin partially esterified with from about 1 to about 7 weightpercent of a naphthoquinonediazidosulfonyl group; b) one or moredilution resins; c) at least one photosensitive component in an amountsufficient to photosensitive said composition; and d) at least onesolvent; ii) coating a suitable substrate with the photoresistcomposition of step i); and iii) heat treating the coated substrate ofstep i) until substantially all of the photoresist solvent is removed;image-wise exposing the photoresist composition and removing theimage-wise exposed areas of such composition with a suitable developer.

DETAILED DESCRIPTION OF THE INVENTION

[0018] The present invention relates to a photoresist composition thatcomprises a composition comprising: a) a novolak resin partiallyesterified with from about 1 to about 7 weight percent of anaphthoquinonediazidosulfonyl group (further from about 3 to about 7weight percent); b) one or more dilution resins; c) at least onephotosensitive compound in an amount sufficient to photosensitive saidcomposition; and d) at least one solvent.

[0019] The partially esterified novolak for the claimed composition is awater-insoluble, alkali-soluble, film forming phenolic resin preferablyhaving a weight average molecular weight from about 1,000 to 30,000,preferably from about 1,500 to 10,000. The DNQ used for partialesterification of the novolak resin contains quinonediazide sulfonylgroups that replace the hydrogen atom of hydroxyl groups in the novolakresin. The one or more dilution resins dilute the amount of partiallyesterified novolak resin in the composition to allow for bettersolution, viscosity, and other physical and chemical benefits in thecomposition and the resulting photoresist. The solvent suitable for usein present invention may be any of those well known to those skilled inthe art; solvent or solvent blends include those selected from2-heptanone, either alone or in combination with anisole; ethyl lactate,either alone or in combination with n-butyl acetate or propylene glycolmethyl ether; or propylene glycol methyl ether, either alone or incombination with ethyl 3-ethoxypropionate.

[0020] The invention further relates to a process of forming an image ona substrate. The substrate is coated with a film of the photoresistcomposition of the instant invention. The photoresist film is imagewiseexposed through a mask with ultraviolet radiation and processed inaccordance with those steps known to those skilled in the art.

[0021] The invention further relates to a method for producing amicroelectronic device by forming an image on a substrate comprising i)providing an admixture of a photoresist composition comprising: a) anovolak resin partially esterified with from about 1 to about 7 weightpercent of a naphthoquinonediazidosulfonyl group; b) one or moredilution resins; c) at least one photosensitive component in an amountsufficient to photosensitize said composition; and d) at least onesolvent; ii) coating a suitable substrate with the photoresistcomposition of step i); iii) heat treating the coated substrate of stepi) until substantially all of the photoresist solvent is removed;image-wise exposing the photoresist composition and removing theimage-wise exposed areas of such composition with a suitable developer.

[0022] Solutions containing partially esterified film-forming novolakresin with DNQ of the claimed composition are extremely viscous and aredifficult to work with in formulating photoresist compositions. It hasbeen found that by adding a dilution resin to a solution containing thepartially esterified novolak resin, viscosity and other physical andchemical properties of the composition improve and the compositionbecomes very useful in forming photoresist.

[0023] The novolak resin that is partially esterified according to thepresent invention is prepared by subjecting a phenol or a substitutedphenol to an addition-condensation reaction of a phenol or substitutedphenol (or a combination thereof) and an aldehyde, including aformaldehyde generating source, or ketone (or a combination thereof), inthe presence of an acid or a divalent metal salt catalyst, in a suitablereaction solvent, as are well known to one skilled in the art ofphotoresists. Suitable phenols include, but are not limited to, phenol,chlorophenols, fluorophenols, m-cresol, o-cresol, p-cresol, m-ethylphenol, o-ethyl phenol, p-ethyl phenol, m-butyl phenol, o-butyl phenol,p-butyl phenol, trimethylsilylphenol, chloromethylphenol, 2,3-xylenol,2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol,3,6-xylenol, o-phenyl phenol, m-phenyl phenol, p-phenyl phenol,2,3,5-trimethylphenol, 2,3,5-triethylphenol, 3,4,5-trimethylphenol,4-tert-butylphenol, 3-tert-butylphenol, 2-tert-butylphenol,2-tert-butyl-4-methyphenol, 2-tert-butyl-5-methylphenol and otheralkyl-substituted phenols; p-methoxyphenol, m-methoxyphenol,o-methoxyphenol, p-ethoxphenol, m-ethoxyphenol, o-ethoxyphenol,o-propoxyphenol, p-propoxyphenol, m-propoxyphenol and otheralkoxy-substituted phenols; o-isopropenylphenol, p-isopropenylphenol,2-methyl-4-isopropenylphenol, 2-ethyl-4-isoprpenylphenol and otherisopropenyl-substituted phenols; phenylphenol and other aryl-substitutedphenols; 4,4′-dihydroxybiphenyl, bisphenol A, hydroquinone, resorcinol,2-methyl resorcinol, 5-methyl resorcinol, pyrogallol, catechol, andothers as are well known to those skilled in the photoresist art. Thesephenols may be used either alone or in an admixture of two or more,depending upon the dissolution rate desired.

[0024] As for examples of the aldehyde, there may be used, either aloneor in combination, those such as formaldehyde, paraformaldehyde,acetaldehyde, benzaldehyde, furfural, trioxane, propionaldehyde,butylaldehyde, trimethylacetaldehyde, acrolein (acrylaldehyde),crotonaldehyde, cyclohexanaldehyde, furylacrolein, terephthalaldehyde,phenylacetaldehyde, α-phenypropyladehyde, β-phenylpropylaldehyde,o-hydroxybenzaldehyde, m-hydroxybenaldehyde, p-hydroxybenzaldehyde,o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde,o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde,cinnamaldehyde, salicylaldehyde, 2-chlorobenzaldehyde,3-chlorobenzaldehyde, 4-chlorobenzaldehyde, 2-hydroxybenzaldehyde,3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2-methoxbenzaldehyde,3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-nitrobenzaldehyde,3-nitrobenzaldehyde, 4-nitrobenzaldehyde, propylaldehyde,phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde,o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde,p-ethylbenzaldehyde, para-n-butylbenzaldehyde, and the like and mixturesthereof. As a formaldehyde-generating source, used are formalin,trioxane, paraformaldehyde, and hemiformals such as methylhemiformal,ethylhemiformal, propylhemiformal, butylhemiformal, andphenylhemiformal.

[0025] Examples of the ketones include acetone, methyl ethyl ketone,diethyl ketone and diphenyl ketone. Each of these ketones may be usedsingly or in combination. Further, an optional combination of any ofaldehydes and any of ketones can be employed.

[0026] As the acid catalyst, there may be utilized inorganic acids suchas hydrochloric acid, nitric acid, sulfuric acid and the like, organicacids such as formic acid, oxalic acid, maleic acid and the like, anddivalent inorganic metal salts of copper, cobalt, magnesium, manganese,nickel, zinc and the like. The reaction solvent is normally ahydrophilic solvent, such as methanol or dioxane. Examples ofalkali-soluble, film forming novolak resins include phenol-formaldehydenovolaks, cresol-formaldehyde novolaks, and phenol-modifiedxylenol-formaldehyde novolaks.

[0027] According to the present invention, a novolak resin is partiallyesterified by replacing from about 1 to about 7 percent (further fromabout 3 to about 7 percent) of the hydrogen atoms of its hydroxyl groupswith a compound containing a naphthoquinonediazidosulfonyl (DNQ) group.Examples of suitable DNQ groups include a1,2-naphthoquinonediazide-4-sulfonyl group, a1,2-naphthoquinonediazide-5-sulfonyl group, a7-methyl-1,2-naphthoquinonediazide-4-sulfonyl group, a2,1-naphthoquinonediazide-4-sulfonyl group, a2,1-naphthoquinonediazide-6-sulfonyl group, a2,1-naphthoquinonediazide-7-sulfonyl group, and a2,1-naphthoquinonediazide-8-sulfonyl group. These DNQ groups may beutilized alone or in combination, but the1,2-naphthoquinonediazide4-sulfonyl group and1,2-naphthoquinonediazide-5-sulfonyl group are particularly preferred.

[0028] One or more dilution resins are added to the present composition.The dilution resins include, for example, the same novolak resins thatare described above in a) except that they are not partially esterifiedwith DNQ. Some of these novolak resins include, among others, acondensation product between trimethylphenol and formaldehyde and acondensation product between acetone and pyrogallol.

[0029] Other dilution resins include polyhydroxy phenol compounds suchas, for example,1,1-bis(4-hydroxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(3,5-dimethyl4-hydroxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(3,5-dimethyl-2-hydoxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(4-hydroxy-3-methylphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(2,6-dimethyl-4-hydroxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(3,4-dihydroxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(3,4,5-trihydroxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,1,1-bis(3,5-dimethyl-2-hydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,1.1-bis(4-hydroxy-3-methylphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,1,1-bis(2,6-dimethyl-4-hydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,1,1-bis(3,4-dihydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,1,1-bis(3,4,5-trihydroxyphenyl)-1-[4-(1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,4,4′,4″,4′″-(1,4-phenylenedimethylidyne)tetrakisphenol,4,4′-[(3-hydroxyphenyl)methylene]bis[2-methylethylphenol],2,2′-[(3-hydroxyphenyl)methylene]bis[3,5,6-trimethylphenol],2,2′-[(2-hydroxy-3-methoxylphenyl)methylene]bis[3,5-dimethylphenol],2,2′-[(4-hydroxy-3-methoxyphenyl)methylene]bis[3,5-dimethylphenol],4-[bis(4-hydroxyphenyl)methyl]-2-ethoxyphenol,4-[bis(4-hydroxyphenyl)methyl]-2-methoxyphenol,2,4,6-tris(4-hydroxyphenylmethyl)-1,3-benzenediol,4,4′-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol,4-(2,3,5-trimethyl-4-hydroxyphenyl)methyl-1,3-benzenediol,6,6′-methylenebis[4-(4-hydroxy-3,5-dimethylphenylmethyl)-1,2,3-benzenetriol],2,6-bis[(2,4-dihydroxyphenyl)methyl]-4-ethylphenol,2,4-bis[(2,4-dihydroxyphenyl)methyl]-6-cyclohexylphenol,2,6-bis[[2,3-dihydroxy-5-(1,1-dimethylethyl)phenyl]methyl]-4-methylphenol,4,4′-[(3,4-dihydroxyphenyl)methylenbis[2-(methylethyl)phenol],2,2′-[(3,4-dihydroxyphenyl)methylene]bis[3,5,6-trimethylphenol],2,2′-[(3-hydroxy-4-methoxyphenyl)methylene]bis[3,5-dimethylphenol],2,4′,4″-methylidynetrisphenol,4,4′-[(2-hydroxyphenyl)methylene]bis[3-methylphenol],4,4′,4″-(3-methyl-1-propanyl-3-ylidene)trisphenol,2,2′-[(3-hydroxyphenyl)methylene]bis[3,5-dimethylphenol],4,4′,4″,4′″-(1,2-ethanediylidene)tetrakisphenol,4,6-bis[(4-hydroxyphenyl)methyl]-1,3-benzenediol,4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2-methylphenol],2,2′-[(2-hydroxyphenyl)methylene]bis[3,5-dimethylphenol],2,2′-[(4-hydroxyphenyl)methylene]bis[3,5-dimethylphenol],(2,4-dihydroxyphenyl)(4-hydroxyphenyl)methane,4-[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-benzenediol,4-[(3,5-dimethyl-4-hydroxyphenyl)methyl]-1,2,3-benzenetriol,4,4′-[1,4-phenylenebis(1-methylethylidene)]bis[benzene-1,2-diol],5,5′-[1,4-phenylenebis(1-methylethylidene)]bis[benzene-1,2,3-triol],4-[(2,3,5-trimethyl-4-hydroxyphenyl)methyl]-1,2,3-benzenetriol,4,4′-methylenebis[6-methylcarbonyl-1,3-benzenediol],6,6′-methylenebis[4-(4-hydroxyphenylmethyl)-1,2,3-benzenetriol],6,6′-ethylidenebis[4-(4-hydroxyphenylcarboxy)-1,2,3-benzenetriol],4,4′,4″-methylidynetris[2,6-bis[(hydroxyphenyl)methyl]phenol],4,4′,4″-ethylidenetris[2,6-bis[(hydroxyphenyl)methyl]phenol],2,2′-bis[(3,4-dihydroxyphenyl)methylene]bis [3,5-dimethylphenol],4-[(4-hydroxyphenyl)methyl]-1,2,3-benzenetriol, and4,4′-[1,4-phenylenebis(1-methylethylidene)]bis[benzene-1,2,3-triol].

[0030] Additional examples of polyhydroxy phenols can be found in U.S.Pat. Nos. 4,863,828; 5,087,548; 5,110,706; 5,238,775; 5,290,658;5,318,875, 5,380,618; 5,397,679; 5,407,778; 5,413,896, 5,429,904,5,429,905, and 5,556,995 and in European published application No. 0 554101, each incorporated herein by reference for disclosure of suitablepolyhydroxy phenols in accordance with this invention. Some polyhydroxyphenols are exemplified by the following formulae:

[0031] wherein R₈, R₂, R₁₀, R₁₁, R₁₂, R₁₃ and R₂₆ are each independentlyhydrogen, an unsubstituted or substituted C₁₋₆ alkyl group, anunsubstituted or substituted C₆₋₁₀ aryl or hydroxyl;

[0032] a, b, c and d are each independently integers from 0 to 5.

[0033] The substituted or unsubstituted alkyl group includes, forexample, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl,cyclohexyl, hydroxymethyl, chloromethyl, bromomethyl, 2-chloromethyl,trimethylsilylmethyl groups, and the like. The substituted orunsubstituted aryl group includes, for example, phenyl, benzyl, cumyl,1-naphthyl, 2-naphthyl, 4-hydroxyphenyl, 4-trimethylsiloxyphenyl,4-methoxyphenyl and 4-acetylphenyl groups, and the like.

[0034] The groups R₈ to R₁₁ bonded to respective benzene rings may bethe same or different and each of R₈ to R₁₁ may comprise two or moredifferent groups, and at least one of the groups R₈, R₉ and R₁₁ containsat least one hydroxy group.

[0035] wherein R₁₂ to R₁₇ are H, halogen, C₁₋₆ alkyl, alkenyl or OH, R₁₈and R₁₉ are H, halogen or C₁₋₆ alkyl, and R₂₀ to R₂₅ are H or C₁₋₆ alkyl

[0036] wherein Y is selected from —C—; —C(CH₃)₂—, or —O—; Z is selectedfrom —C— or —C(CH₃)₂—; and each of j, k and q is independently aninteger of 0 to 3 (provided that all of j, k and q cannot be zero), andeach of m, o and r is independently an integer of 0 to 3 (provided thatnone of (j+m), (k+o) and (q+r) exceed four).

[0037] The amount of the dilution resin that is added to the photoresistcomposition generally is from about 1.5 to about 20 percent of thesolids of the photoresist composition, generally depending upon thedesired film thickness. Generally, for film thicknesses up to andincluding about 2 μm, the amount of dilution resin added to thephotoresist composition is from about 1.5 to about 6 percent, furtherfrom about 2 to about 4 percent, of the solids of the photoresistcomposition. Generally, for film thicknesses greater than 2 μm, theamount of dilution resin added to the photoresist composition is fromabout 6 to about 20 percent of the solids of the photoresistcomposition.

[0038] One or more photosensitive compounds are added to the presentcomposition. Examples of photosensitive compounds include, for example,one or more of (1) a reaction product between anaphthoquinonediazidesulfonyl halide (for example,1,2-naphthoquinonediazide-5-sulfonyl halide,7-methyl-1,2-naphthoquinonediazide-4-sulfonyl halide,2,1-naphthoquinonediazide-4-sulfonyl halide,2,1-naphthoquinonediazide-6-sulfonyl halide,2,1-naphthoquinonediazide-7-sulfonyl group, and2,1-naphthoquinonediazide-8-sulfonyl halide) orbenzoquinonediazidesulfonyl halide to react with a low-molecular orhigh-molecular compound having at least one functional group capable ofcondensation reaction with these sulfonyl halides. The functional groupthat can be condensed with a sulfonyl halide includes a hydroxyl group,an amino group, and the like. Among these, a hydroxyl group isparticularly preferable and two hydroxyl groups are more preferred. Thecompounds containing a hydroxyl group include, for example,hydroquinone; resorcinol; phenol, p-methoxyphenol, dimethylphenol,bisphenol A, naphthol, pyrocatechol, pyrogallol monomethyl ether,pyrogallol-1,3-dimethyl ether, gallic acid, partially esterified orpartially etherified gallic acid and other phenols;2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone,2,4,6-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone,2,3,4,4′-tetrahydroxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenoneand 2,2′,3,4,6′-pentahydroxybenzophenone,2,3′,4,4′,6-pentahydroxybenzophenone,2,2′,3,4,4′-pentahydroxybenzophenone,2,2′,3,4,5′-pentahydroxybenzophenone,2,3′,4,5,5′-pentahydroxybenzophenone,2,3,3′,4,4′,5′-hexahydroxybenzophenone and otherpolyhydroxybenzophenones; hydroxyphenylalkanes such asbis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane andbis(2,4-dihydroxyphenyl)propane; hydroxytriphenylmethanes such as4,4′,3″,4″-tetrahydroxy-3,5,3′,5′-tetramethylphenylmethane and4,4′,2″,3″,4″-pentahydroxy-3,5,3′,5′-tetramethyltriphenylmethane;bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane,bis[3-(3,5-dimethyl4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl]methane,bis[3-(3,5-diethyl-4-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane,bis[3-(3,5-diethyl-4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl]methane andother terminal xylenol linear tetranuclear compounds;2,4-bis[2-hydroxy-3-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenol,2,4-bis[4-hydroxy-3-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenoland other linear pentanuclear compounds and other linear polyphenoliccompounds;bis[2-hydroxy-3-(3,5-dimethyl-4-hydroxybenzyl)-5-methylphenyl]methane,bis[2-hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-methylphenyl]methane,bis[4-hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-methylphenyl]methane,bis[2,5-dimethyl-3-(4-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane,bis[2,5-dimethyl-3-(4-hydroxybenzyl)-4-hydroxyphenyl]methane,bis[2,5-dimethyl-3-(2-hydroxybenzyl)-4-hydroxyphenyl]methane and otherlinear tetranuclear compounds;1,1-bis(4-hydroxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(3,5-dimethyl-2-hydoxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(4-hydroxy-3-methylphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(2,6-dimethyl-4-hydroxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(3,4-dihydroxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(3,4,5-trihydroxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(4-hydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,1,1-bis(3,5-dimethyl-2-hydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,1.1-bis(4-hydroxy-3-methylphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,1,1-bis(2,6-dimethyl-4-hydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,1,1-bis(3,4-dihydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,1,1-bis(3,4,5-trihydroxyphenyl)-1-[4-(1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,and other non-linear tetranuclear compounds;bis(4-hydroxy-2,3,5-trimethylphenyl)-2-hydroxyphenylmethane,1,4-bis[1-(3,5-dimethyl-4-hydroxyphenyl)isopropyl]benzene,2,4-bis(3,5-dimethyl-4-hydroxyphenylmethyl)-6-methylphenol,bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane,bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane,bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane,1-[1-(4-hydroxyphenyl)isopropyl]4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene,1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl-4-hydroxyphenyl)ethyl]benzene,2,6-bis[1-(2,4-dihydroxyphenyl)isopropyl]-4-methylphenol,4,6-bis[1-(4-hydroxyphenyl)isopropyl]resorcin,4,6-bis(3,5-dimethoxy-4-hydroxyphenylmethyl)pyrogallol,4,6-bis(3,5-dimethyl-4-hydroxyphenylmethyl)pyrogallol,2,6-bis(3-methyl-4,6-dihydroxyphenylmethyl)-4-methylphenol,2,6-bis(2,3,4-trihydroxyphenylmethyl)-4-methylphenol,1,1-bis(4-hydroxyphenyl)cyclohexane and other hydroxyaryls.

[0039] Another example includes (2) the compounds shown in formulae (I)and (II) below:

[0040] wherein R₃, R₄ and R₅ are independently selected from the groupconsisting of a hydrogen atom, a 1,2-naphthoquinonediazide-4-sulfonylgroup, a 1,2-naphthoquinonediazide-5-sulfonyl group, a7-methyl-1,2-naphthoquinonediazide-4-sulfonyl group, a2,1-naphthoquinonediazide-4-sulfonyl group, a2,1-naphthoquinonediazide-6-sulfonyl group, a2,1-naphthoquinonediazide-7-sulfonyl group, a2,1-naphthoquinonediazide-8-sulfonyl group, and mixtures thereof, andR₃, R₄ and R₅ cannot be a hydrogen atom at the same time, R_(6a),R_(6b), R_(6c), R_(7a), R_(7b), R_(7c), and R_(7d) are independentlyselected from a hydrogen atom or C₁₋₄ alkyl group, and n represents 1 or2.

[0041] Examples of compounds of formula (II) include

[0042] where R₃ and R₅ are not hydrogen.

[0043] Examples of the compounds of formula (II) include

[0044] where DNQ is 2,1-diazonaphthoquinone-5-sulfonyl-.

[0045] Typically, the amount of the photosensitive compound added to thephotoresist composition generally is in the amount of from about 2 toabout 6 percent, further from about 2.5 to about 5 percent, of thesolids of the photoresist composition.

[0046] The solvent utilized in the compositions of the present inventionincludes, for example, solvents such a glycol ether derivative such asethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether,diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,dipropylene glycol dimethyl ether, propylene glycol n-propyl ether, ordiethylene glycol dimethyl ether; a glycol ether ester derivative suchas ethyl cellosolve acetate, m ethyl cellosolve acetate, or propyleneglycol monomethyl ether acetate; carboxylates such as ethyl acetate,n-butyl acetate and amyl acetate; carboxylates of di-basic acids such asdiethyloxylate and diethylmalonate; dicarboxylates of glycols such asethylene glycol diacetate and propylene glycol diacetate; and hydroxycarboxylates such as methyl lactate, ethyl lactate, ethyl glycolate, andethyl-3-hydroxy propionate; a ketone ester such as methyl pyruvate orethyl pyruvate; an alkoxycarboxylic acid ester such as methyl3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl2-hydroxy-2-methylpropionate, or methylethoxypropionate; a ketonederivative such as methyl ethyl ketone, acetyl acetone, cyclopentanone,cyclohexanone or 2-heptanone; a ketone ether derivative such asdiacetone alcohol methyl ether; a ketone alcohol derivative such asacetol or diacetone alcohol; lactones such as butyrolactone; an amidederivative such as dimethylacetamide or dimethylformamide, anisole, andmixtures thereof. Solvent or solvent blends can be selected from2-heptanone, either alone or in combination with anisole; ethyl lactate,either alone or in combination with n-butyl acetate or propylene glycolmethyl ether; or propylene glycol methyl ether, either alone or incombination with ethyl 3-ethoxypropionate. When used in combination, themixing weight ratio is usually from about 10:0 to about 0:10, morepreferably from about 9:1 to about 7:3. Typically, the amount of solventadded to the photoresist composition is such that the total amount ofsolids ranges from about 2 percent to about 50 percent.

[0047] According to the present invention, a novolak resin is partiallyesterifed with from about 3 to about 7 weight percent of a DNQ group.The esterified novolak resin is utilized as the film-forming resin in aphotoresist composition. With an addition of the dilution resins, theesterification range of DNQ is generally reduced by up to about 20%

[0048] In addition, in one embodiment of the present invention, the useof the photoresist solvent mixtures provides a photoresist compositioncapable of forming a film of the desired thickness on a substrate at amuch lower solids level in the photoresist composition. The solids levelincludes the partially esterified novolak resin, the one or moredilution resins, and optional solid additives.

[0049] The photoresist composition may also contain various ingredientswell known to those skilled in the art, such as, colorants, dyes,photoactive compounds antistriation agents, leveling agents,plasticizers, adhesion promoters, speed enhancers, solvents and suchsurfactants as nonionic surfactants which may be added to thecomposition of the present invention before the composition is coatedonto a substrate. Examples of dye additives that may be used togetherwith the photoresist compositions of the present invention includeMethyl Violet 2B (C.I. No. 42535), Crystal Violet (C.I. 42555),Malachite Green (C.I. No. 42000), Victoria Blue B (C.I. No. 44045) andNeutral Red (C.I. No. 50040)

[0050] The prepared composition can be applied to a substrate by anyconventional method used in the photoresist art, including, for example,dipping, spraying, whirling, spin coating, Myrad bar, gravure, doctorblade, slot coating or slit (or die) coating, or similar devices. Whenspin coating, for example, the photoresist solution can be adjusted withrespect to the percentage of solids content in order to provide coatingof the desired thickness given the type of spinning equipment utilizedand the amount of time allowed for the spinning process.

[0051] A microelectronic device can be formed by forming an image on asubstrate comprising i) providing an admixture of a photoresistcomposition comprising: a) a novolak resin partially esterified withfrom about 1 to about 7 weight percent of anaphthoquinonediazidosulfonyl group; b) one or more dilution resins; c)at least one photosensitive component in an amount sufficient tophotosensitize said composition; and d) at least one solvent; ii)coating a suitable substrate with the photoresist composition of stepi); and iii) heat treating the coated substrate of step i) untilsubstantially all of the photoresist solvent is removed; image-wiseexposing the photoresist composition and removing the image-wise exposedareas of such composition with a suitable developer.

[0052] Suitable substrates include silicon, aluminum, polymeric resins,silicon dioxide, doped silicon dioxide, silicon nitride, tantalum,copper, polysilicon, ceramics, aluminum/copper mixtures; galliumarsenide and other such Group IIIN compounds. The photoresist coatingsproduced by the above described procedure are particularly suitable forapplication to thermally grown silicon/silicon dioxide-coated waferssuch as are utilized in the production of microelectronic devices suchas microprocessors and other miniaturized integrated circuit components.The photoresist compositions of the present invention are also useful inthe manufacture of other microelectronic devices, such as flat paneldisplays (for example and including, but not limited to liquid crystaldisplays, plasma display panels, thin film electroluminescent displays,organic luminescent displays, plasma addressed liquid crystal displaysand the like), used in, for example, computer display monitors,televisions, and the like. An aluminum/aluminum oxide wafer can be usedas well. The substrate may also comprise various polymeric resinsespecially transparent polymers such as polyesters. The substrate mayhave an adhesion promoted layer of a suitable composition such as onecontaining hexa-alkyl disiiazane.

[0053] The photoresist composition solution is then coated onto thesubstrate, and the substrate is temperature treated at from about 80° C.to about 110° C. for from about 30 seconds to about 180 seconds on a hotplate or for from about 15 to about 40 minutes in a convection oven.This temperature treatment is selected in order to reduce theconcentration of residual solvents in the photoresist while not causingsubstantial thermal degradation of the composition components. Ingeneral one desires to minimize the concentration of solvents and thusthis first temperature treatment is conducted until substantially all ofthe solvents have evaporated and a thin coating of photoresistcomposition, on the order of a micron in thickness, remains on thesubstrate. In a preferred embodiment the temperature is conducted atfrom about 85° C. to about 95° C. The treatment is conducted until therate of change of solvent removal becomes relatively insignificant. Thetemperature and time selection depends on the photoresist propertiesdesired by the user as well as equipment used and commercially desiredcoating times. The coating substrate can then be exposed to actinicradiation, especially ultraviolet radiation, at a wavelength of fromabout 150 nm to about 450 nm, x-ray, electron beam, ion beam or laserradiation, in any desired pattern, produced by use of suitable masks,negatives, stencils, templates, etc.

[0054] The photoresist is then optionally subjected to a post exposuresecond baking or heat treatment either before or after development. Theheating temperatures may range from about 90° C. to about 150° C., morepreferably from about 110° C. to about 150° C. The heating may beconducted for from about 10 seconds to about 30 minutes, more preferablyfrom about 45 seconds to about 90 seconds on a hot plate or about 10 toabout 30 minutes by convection oven.

[0055] The exposed photoresist-coated substrates are developed to removethe imagewise exposed, non-image areas by spray developing using analkaline developing solution. The solution is preferably agitated, forexample, by nitrogen burst agitation. The substrates are allowed toremain in the developer until all, or substantially all, of thephotoresist coating has dissolved from the exposed areas. Developers mayinclude aqueous solutions of ammonium or alkali metal hydroxides. Onepreferred hydroxide is tetramethyl ammonium hydroxide. A suitabledeveloper is AZ 300 MIF Developer available commercially from theClariant Corporation, Somerville, N.J. After removal of the coatedwafers from the developing solution, one may conduct an optionalpost-development heat treatment or bake in increase the coating'sadhesion and chemical photoresistance to etching solutions and othersubstances. The postdevelopment heat treatment can comprise the ovenbaking of the coating and substrate below the coating's softening point.The industrial applications, for example in the manufacture ofmicrocircuitry units on, for example, silicon/silicon dioxide typesubstrates, the developed substrates may be treated with a buffered,hydrofluoric acid base etching solution. The photoresist compositions ofthe present invention are resistant to acid-base etching solutions andprovide effective protection for the unexposed photoresist-coating areasof the substrate. The photoresist compositions of the present inventionare also useful in the manufacture of other microelectronic units, suchas flat panel displays (for example and including, but not limited toliquid crystal displays, plasma display panels, thin filmelectroluminescent displays, organic luminescent displays, plasmaaddressed liquid crystal displays and the like), used in, for example,computer display monitors, televisions, and the like.

[0056] Examples of the present invention are set forth below, by way ofillustration and not limitation. Unless otherwise noted, all parts andpercentages herein are by weight; molecular weight is weight averagemolecular weight, all temperatures are degrees Centigrade.

Example A

[0057] A meta-cresol/para-cresol novolak resin was reacted withsufficient amount of 1,2-naphthoquinonediazide-5-sulfonyl chloride underappropriate reaction conditions to form a novolak resin that waspartially esterified, at 4.5%, with 1,2-naphthoquinonediazide-5-sulfonylgroups.

Example 1

[0058] 9.55 grams of the resin from Example A was blended with 0.2 gramsof a dilution resin (a 1:1 ratio of4,4′-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol(TPPA) and an m-cresol:p-cresol:trimethylphenol (3:5:2parts)/formaldehyde resin) and 0.25 grams of a photosensitive compound(reaction product between DNQ and formula (IIB) above where R₃ and R₅are DNQ). The resulting blend was then diluted to 30% active solids in2-heptanone.

Example 2

[0059]9.1 grams of the resin from Example A was blended with 0.4 gramsof a dilution resin (a 1:1 ratio of4,4′-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol(TPPA) and an m-cresol:p-cresol:trimethylphenol (3:5:2parts)/formaldehyde resin) and 0.5 grams of a photosensitive compound(reaction product between DNQ and formula (IIB) above where R₃ and R₅are DNQ). The resulting blend was then diluted to 30% active solids in2-heptanone.

[0060] The compositions of Example 1 and Example 2 were individuallyapplied to silicon wafers at 4,000 rpm and then soft-baked on aproximity hotplate oven at 90° C. for about 60 seconds to form a filmthickness of 12,000 Å. Actinic exposure was applied using an ASML i-250stepper, annular exposure, 0.6 NA, through a glass photomask containinga resolution test pattern. The coated wafers were exposed at varyingdoses ranging from 210 mJ/cm² to 260 mJ/cm² with nominal exposure for 5μm is 180 mJ/cm².

[0061] After exposure, the wafers were post exposure baked on aproximity hot plate at 110° C. for about 60 seconds.

[0062] The wafers were subsequently developed with AZ 300 MIF Developerusing a single puddle at 23° C. for about 60 seconds.

[0063] The formulations of Example 1 and Example 2 resulted in goodlithographic performance with improved resolution and profile.

[0064] While described in terms of the presently preferred embodiments,it is to be understood that the present disclosure is to be interpretedas by way of illustration, and not by way of limitation, and thatvarious modifications and alterations apparent to one skilled in the artmay be made without departing from the scope and spirit of the presentinvention.

1. A composition comprising: a) a novolak resin partially esterifiedwith from about 1 to about 7 weight percent of anaphthoquinonediazidosulfonyl group; b) one or more dilution resins; c)at least one photosensitive component in an amount sufficient tophotosensitize said composition; and d) at least one solvent.
 2. Thecomposition of claim 1 wherein a) the novolak resin is partiallyesterified from about 3 to about weight percent of anaphthoquinonediazidosulfonyl group.
 3. The composition of claim 1wherein for a) the naphthoquinonediazidosulfonyl group is selected from1,2-naphthoquinonediazide-4-sulfonyl group, a1,2-naphthoquinonediazide-5-sulfonyl group, a7-methyl-1,2-naphthoquinonediazide-4-sulfonyl group, a2,1-naphthoquinonediazide-4-sulfonyl group, a2,1-naphthoquinonediazide-6-sulfonyl group, a2,1-naphthoquinonediazide-7-sulfonyl group, and a2,1-naphthoquinonediazide-8-sulfonyl group.
 4. The composition of claim3 wherein for a) the naphthoquinonediazidosulfonyl group is a1,2-naphthoquinonediazide-4-sulfonyl group or a1,2-naphthoquinonediazide-5-sulfonyl group.
 5. The composition of claim1 wherein b) one or more dilution resins is selected from the groupconsisting of a non-esterified novolak resin, polyhydroxy phenols, andmixtures thereof.
 6. The composition of claim 5 wherein b) one or moredilution resins is a mixture of a non-esterified novolak resin andpolyhydroxy phenols.
 7. The composition of claim 6 wherein b) thepartially esterified novolak resin is selected from a resin formed by acondensation reaction between trimethylphenol and formaldehyde, a resinformed by a condensation reaction between acetone and pyrogallol, aresin formed by a condensation reaction between m-cresol, p-cresol,trimethylphenol, and formaldehyde or mixtures thereof.
 8. Thecomposition of claim 7 wherein the polyhydroxy phenols is selected fromthe group consisting of1,1-bis(4-hydroxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(3,5-dimethyl-2-hydoxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(4-hydroxy-3-methylphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(2,6-dimethyl-4-hydroxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(3,4-dihydroxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(3,4,5-trihydroxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,1,1-bis(3,5-dimethyl-2-hydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,1.1-bis(4-hydroxy-3-methylphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,1,1-bis(2,6-dimethyl-4-hydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,1,1-bis(3,4-dihydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,1,1-bis(3,4,5-trihydroxyphenyl)-1-[4-(1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,4,4′,4″,4′″-(1,4-phenylenedimethylidyne)tetrakisphenol,4,4′-[(3-hydroxyphenyl)methylene]bis[2-methylethylphenol],2,2′-[(3-hydroxyphenyl)methylene]bis[3,5,6-trimethylphenol],2,2′-[(2-hydroxy-3-methoxylphenyl)methylene]bis[3,5-dimethylphenol],2,2′-[(4-hydroxy-3-methoxyphenyl)methylene]bis[3,5-dimethylphenol],4-[bis(4-hydroxyphenyl)methyl]-2-ethoxyphenol,4-[bis(4-hydroxyphenyl)methyl]-2-methoxyphenol,2,4,6-tris(4-hydroxyphenylmethyl)-1,3-benzenediol,4,4′-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol,4-(2,3,5-trimethyl-4-hydroxyphenyl)methyl-1,3-benzenediol,6,6′-methylenebis[4-(4-hydroxy-3,5-dimethylphenylmethyl)-1,2,3-benzenetriol],2,6-bis[(2,4-dihydroxyphenyl)methyl]-4-ethylphenol,2,4-bis[(2,4-dihydroxyphenyl)methyl]-6-cyclohexylphenol,2,6-bis[[2,3-dihydroxy-5-(1,1-dimethylethyl)phenyl]methyl]-4-methylphenol,4,4′-[(3,4-dihydroxyphenyl)methylen]bis[2-(methylethyl)phenol],2,2′-[(3,4-dihydroxyphenyl)methylene]bis[3,5,6-trimethylphenol],2,2′-[(3-hydroxy-4-methoxyphenyl)methylene]bis[3,5-dimethylphenol],2,4′,4″-methylidynetrisphenol,4,4′-[(2-hydroxyphenyl)methylene]bis[3-methylphenol],4,4′,4″-(3-methyl-1-propanyl-3-ylidene)trisphenol,2,2′-[(3-hydroxyphenyl)methylene]bis[3,5-dimethylphenol],4,4′,4″,4′″-(1,2-ethanediylidene)tetrakisphenol,4,6-bis[(4-hydroxyphenyl)methyl]-1,3-benzenediol,4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2-methylphenol],2,2′-[(2-hydroxyphenyl)methylene]bis[3,5-dimethylphenol],2,2′-[(4-hydroxyphenyl)methylene]bis[3,5-dimethylphenol],(2,4-dihydroxyphenyl)(4-hydroxyphenyl)methane,4-[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-benzenediol,4-[(3,5-dimethyl-4-hydroxyphenyl)methyl]-1,2,3-benzenetriol,4,4′-[1,4-phenylenebis(1-methylethylidene)]bis[benzene-1,2-diol],5,5′-[1,4-phenylenebis(1-methylethylidene)]bis[benzene-1,2,3-triol],4-[(2,3,5-trimethyl-4-hydroxyphenyl)methyl]-1,2,3-benzenetriol,4,4′-methylenebis[6-methylcarbonyl-1,3-benzenediol],6,6′-methylenebis[4-(4-hydroxyphenylmethyl)-1,2,3-benzenetriol],6,6′-ethylidenebis[4-(4-hydroxyphenylcarboxy)-1,2,3-benzenetriol],4,4′,4″-methylidynetris[2,6-bis[(hydroxyphenyl)methyl]phenol],4,4′,4″-ethylidenetris[2,6-bis[(hydroxyphenyl)methyl]phenol],2,2′-bis[(3,4-dihydroxyphenyl)methylene]bis [3,5-dimethylphenol],4-[(4-hydroxyphenyl)methyl]-1,2,3-benzenetriol, and4,4′-[1,4-phenylenebis(1-methylethylidene)]bis[benzene-1,2,3-triol]. 9.The composition of claim 8 wherein b) is a mixture between a resinformed by a condensation reaction between m-cresol, p-cresol,trimethylphenol, and formaldehyde and4,4′-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol.10. The composition of claim 5 wherein b) is a mixture of non-esterifiednovolak resins.
 11. The composition of claim 10 wherein b) is a mixtureof any two resins formed by a condensation reaction betweentrimethylphenol and formaldehyde, a resin formed by a condensationreaction between acetone and pyrogallol, a condensation reaction betweenxylenol, m- and/or p-cresol, and formaldehyde, or a resin formed by acondensation reaction between m-cresol, p-cresol, trimethylphenol, andformaldehyde.
 12. The composition of claim 1 wherein the photosensitivecompound is selected from a reaction product between anaphthoquinonediazidesulfonyl halide or benzoquinonediazidesulfonylhalide and a compound containing at least one hydroxyl group selectedfrom hydroquinone; resorcinol; phenol, p-methoxyphenol, dimethylphenol,bisphenol A, naphthol, pyrocatechol, pyrogallol monomethyl ether,pyrogallol-1,3-dimethyl ether, gallic acid, partially esterified orpartially etherified gallic acid and other phenols;2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone,2,4,6-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone,2,3,4,4′-tetrahydroxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone,2,2′,3,4,6′-pentahydroxybenzophenone,2,3′,4,4′,6-pentahydroxybenzophenone,2,2′,3,4,4′-pentahydroxybenzophenone,2,2′,3,4,5′-pentahydroxybenzophenone,2,3′,4,5,5′-pentahydroxybenzophenone,2,3,3′,4,4′,5′-hexahydroxybenzophenone and otherpolyhydroxybenzophenones; bis(2,4-dihydroxyphenyl)methane,bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)propane andother hydroxyphenylalkanes;4,4′,3″,4″-tetrahydroxy-3,5,3′,5′-tetramethylphenylmethane,4,4′,2″,3″,4″-pentahydroxy-3,5,3′,5′-tetramethyltriphenylmethane andother hydroxytriphenylmethanes;bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane,bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl]methane,bis[3-(3,5-diethyl-4-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane,bis[3-(3,5-diethyl-4-hydroxybenzyl)4-hydroxy-5-ethylphenyl]methane andother terminal xylenol linear tetranuclear compounds;2,4-bis[2-hydroxy-3-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenol,2,4-bis[4-hydroxy-3-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenoland other linear pentanuclear compounds and other linear polyphenoliccompounds; bis[2-hydroxy-3-(3,5-dimethyl-4-hydroxybenzyl)-5-methylphenyl]methane,bis[2-hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-methylphenyl]methane,bis[4-hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-methylphenyl]methane,bis[2,5-dimethyl-3-(4-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane,bis[2,5-dimethyl-3-(4-hydroxybenzyl)-4-hydroxyphenyl]methane,bis[2,5-dimethyl-3-(2-hydroxybenzyl)-4-hydroxyphenyl]methane and otherlinear tetranuclear compounds;1,1-bis(4-hydroxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(3,5-dimethyl-2-hydoxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(4-hydroxy-3-methylphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(2,6-dimethyl-4-hydroxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(3,4-dihydroxyphenyl)-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(3,4,5-trihydroxyphenyl )-1-[4-(4-hydroxybenzyl)phenyl]ethane,1,1-bis(4-hydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,1,1-bis(3,5-dimethyl-2-hydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,1.1-bis(4-hydroxy-3-methylphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,1,1-bis(2,6-dimethyl-4-hydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,1,1-bis(3,4-dihydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,1,1-bis(3,4,5-trihydroxyphenyl)-1-[4-(1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane,and other non-linear tetranuclear compounds;bis(4-hydroxy-2,3,5-trimethylphenyl)-2-hydroxyphenylmethane,1,4-bis[1-(3,5-dimethyl-4-hydroxyphenyl)isopropyl]benzene,2,4-bis(3,5-dimethyl-4-hydroxyphenylmethyl)-6-methylphenol,bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane,bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane,bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane,1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene,1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl-4-hydroxyphenyl)ethyl]benzene,2,6-bis[1-(2,4-dihydroxyphenyl)isopropyl]-4-methylphenol,4,6-bis[1-(4-hydroxyphenyl)isopropyl]resorcin,4,6-bis(3,5-dimethoxy-4-hydroxyphenylmethyl)pyrogallol,4,6-bis(3,5-dimethyl-4-hydroxyphenylmethyl)pyrogallol,2,6-bis(3-methyl-4,6-dihydroxyphenylmethyl)-4-methylphenol,2,6-bis(2,3,4-trihydroxyphenylmethyl)-4-methylphenol,1,1-bis(4-hydroxyphenyl)cyclohexane and other hydroxyaryls, and acompound represented by formula (I) or (II)

wherein R₃, R₄ and R₅ are independently selected from the groupconsisting of a hydrogen atom, a 1,2-naphthoquinonediazide-4-sulfonylgroup, a 1,2-naphthoquinonediazide-5-sulfonyl group, a7-methyl-1,2-naphthoquinonediazide-4-sulfonyl group, a2,1-naphthoquinonediazide-4-sulfonyl group, a2,1-naphthoquinonediazide-6-sulfonyl group, a2,1-naphthoquinonediazide-7-sulfonyl group, a2,1-naphthoquinonediazide-8-sulfonyl group, and mixtures thereof, andR₃, R₄ and R₅ cannot be a hydrogen atom at the same time, R_(6a),R_(6b), R_(6c), R_(7a), R_(7b), R_(7c), and R_(7d) are independentlyselected from a hydrogen atom or C₁₋₄ alkyl group, and n represents 1 or2.
 13. The composition of claim 12 wherein b) the photosensitivecompound is selected from

where DNQ is 2,1-diazonaphthoquinone-5-sulfonyl-.
 14. The composition ofclaim 1 wherein d) at least one solvent is selected from 2-heptanone,anisole, ethyl lactate, n-butyl acetate, propylene glycol methyl ether,propylene glycol methyl ether, ethyl 3-ethoxypropionate and mixturesthereof.
 15. The composition of claim 1 wherein d) at least one solventis 2-heptanone.
 16. The composition of claim 1 wherein d) at least onesolvent is a mixture of ethyl lactate and with n-butyl acetate.
 17. Thecomposition of claim 1 wherein d) at least one solvent is and propyleneglycol methyl ether acetate.
 18. A process for preparing a compositioncomprising providing an admixture of: a composition comprising: a) anovolak resin partially esterified with from about 1 to about 7 weightpercent of a naphthoquinonediazidosulfonyl group; b) one or moredilution resins; c) at least one photosensitive component in an amountsufficient to photosensitize said composition; and d) at least onesolvent.
 19. The process of claim 18 wherein for a) the novolak resin ispartially esterified with from about 3 to about 7 weight percent of anaphthoquinonediazidosulfonyl group.
 20. A process for forming an imageon a substrate comprising coating a substrate with a compositionaccording to claim 1; imagewise exposing through a mask with ultravioletradiation; and developing the exposed photoresist composition with adeveloper.
 21. A method for producing a microelectronic device byforming an image on a substrate comprising: i) providing an admixture ofa photoresist composition comprising: a) a novolak resin partiallyesterified with from about 1 to about 7 weight percent of anaphthoquinonediazidosulfonyl group; b) one or more dilution resins; c)at least one photosensitive component in an amount sufficient tophotosensitive said composition; and d) at least one solvent ii) coatinga suitable substrate with the photoresist composition of step i); andiii) heat treating the coated substrate of step ii) until substantiallyall of the photoresist solvent is removed; image-wise exposing thephotoresist composition and removing the image-wise exposed areas ofsuch composition with a suitable developer.